CA3171204A1 - Composite material comprising a fluorinated amide and uses in electrochemical cells - Google Patents

Abstract

The present technology relates to a composite material comprising inorganic particles, a fluorinated amide compound, and optionally an electrolyte polymer, a plasticizer and/or a salt, as well as the method for preparing the composite material. Also described are solid electrolytes and electrode materials comprising the present composite material and their use in electrochemical cells and accumulators comprising them.

Description

COMPOSITE MATERIAL COMPRISING A FLUORINATED AMIDE AND
USES IN ELECTROCHEMICAL CELLS
RELATED REQUEST
This application claims priority, under applicable law, of the request of Canadian patent number 3,122,820 filed on June 18, 2021, the content of which is incorporated herein by reference in its entirety and to all purposes.
TECHNICAL AREA
The present application relates to polymer-composite electrolytes ceramic comprising an organic additive, their manufacturing processes and to electrochemical cells comprising them.
STATE OF THE TECHNIQUE
Lithium ion-conducting polymer electrolytes enable the development of safer and more affordable manufacturing processes, which are easily scaled to all-solid state batteries of large format (for example, see US Patent Number 6,903,174).
However, the low ionic conductivity limits its application at temperature ambient and results in relatively low charge/discharge rates by compared to conventional lithium-ion batteries.
On the other hand, solid inorganic electrolytes are candidates promising for solid-state batteries because they provide conductivity of lithium ions higher which is comparable to liquid electrolytes. Furthermore, the property of Single ion conduction of inorganic electrolytes allows polarization of lower concentration at the interface of metallic lithium and allows a charge and high speed battery discharge. Despite its conductivity ionic high in densified mass phase, complete cells using Ceramic solid electrolytes suffer from poor performance electrochemical due to significant interface resistance to seals grains of ceramic particles and between the particles of the electrodes composites made up of a mixture of particles of active material, additive of carbon and solid electrolyte. As the conduction of Li + ions must be performed in particle-to-particle mode, the electrochemical performances are limited by the poor distribution of solid electrolyte particles as well as by the existence of vacuum between particles.
A recent review of different composite electrolytes, including a polymer and solid electrolyte particles, was published by the group of S.
Tang et al. (Adv. Energy Mater., 2021, 11, 2000802 (pages 1 to 29)). In order to to improve ionic conductivity, different organic solvents (such as of the carbonate esters) and other plasticizers (such as 1-propene-1,3-sultone, the glycerin, tetraethylene glycol dimethyl ether (TEGDME) Or hexafluoropropylene (HFP)) can be added to the composite. These can however reduce the mechanical strength, for example, if they are present in excess large quantity. Electrochemical instability problems can also be encountered with these composite electrolytes, particularly at the interface enter here electrolyte layer and one of the electrodes, for example an electrode of lithium metallic. In fact, according to Tang et al., despite the progress made in level of composite electrolytes, these always face different challenges in level of ionic conductivity, electrochemical stability and interactions interfacial.
The team of Zhu et al. also recently described some strategies that can be used to increase ionic conductivity and compatibility interracial solid inorganic-organic composite electrolytes (see Energy Storage Materials, 2021, 36, 291-308). Among the strategies for increasing ionic conductivity, we count the adjustment of the particle content inorganic, optimization of particle size and morphology, the orientation of inorganic particles, the modification of the surface of inorganic particles (as with polydopamine, silanes, etc.), or the addition of additives such as plasticizers in the form of small molecules (such as

2 succinonitrile, TEGDME, etc.). Strategies for improving compatibility interfacial solid composite electrolytes described include symmetric or asymmetric multilayer configurations, interactions between polymer (such as polycaprolactone) and inorganic particles, blends of two different polymers (such as poly(ethylene oxide) (POE) and boronized poly(ethylene glycol) (BPEG)) with particles, etc.
There is therefore a constant need for the development of solid electrolytes including the advantages linked to these in general while improving at least one of the aspects mentioned above.
SUMMARY
According to a first aspect, the present technology relates to a material composite comprising inorganic particles, a fluorinated compound, and optionally A
polymer, the fluorinated compound being of Formula I:

H
Formula I
in which :
R1 and R2 are chosen independently at each occurrence from a optionally substituted linear or branched Ci-salkyl group, a C3- group optionally substituted 8cyc10a1ky1e, optionally C6aryl substituted, an optionally substituted C3-8heterocycloalkyl group, and a band optionally substituted C6-6heteroaryl;
X1 is chosen from 0 and NH or Xi is absent;
X2 is chosen from C(0), S(0)2, and Si(R3R4), where R3 and R4 are independently at each occurrence a linear or branched C1-8a1ky1e group optionally substituted, or X2 is absent;

3 in which at least one of R1, R2, R3 and R4 is a group substituted by one or more fluorine atom(s).
According to one embodiment, X1 is absent and X2 is chosen from C(0), S(0)2, and If(R3R4), or XI is chosen from 0 and NH and X2 is absent, or XI and X2 are both absent.
According to another embodiment, R1 is a group substituted by one or several fluorine atom(s), for example, R1 may be a perfluorinated group. In a mode embodiment, R1 is a linear or branched Cl-salkyl group, or a group This-linear or branched 4a1ky1e, or a Ci-2a1ky1e group.
In some embodiments, R2 is a group substituted with one or several fluorine atom(s), for example, R2 may be a perfluorinated group. According to a fashion embodiment, R2 is a linear or branched Cl-salkyl group, or a group This-linear or branched 4a1ky1e, or a C1-2a1ky1e group. Alternatively, R2 is A
optionally substituted C3-8cyc10a1ky1e group, or a C3-6cyc10a1ky1e group optionally substituted, or a C5-6cyc10a1ky1e group optionally substituted.
In certain embodiments, the fluorinated compound is chosen from compounds N-methyltrifluoroacetamide (NMTFAm), N-methylpentaproprionamide (NMPPPAm), N-cylcopentyltrifluoroacetamide (NCPTFAm), NOT-trifluoromethylsulfonyl trifluoroacetamide (NTFMSTFAm), N-trimethylsilyl trifluoroacetamide (NTMSTFAm), and bistrifluoroacetamide (BTFAm).
In one embodiment, the concentration of the compound in the material composite is in the range of 1% to 90% by weight, or 1% to 70% by weight, or from 1% to 50% by weight, or from 1% to 40% by weight, or from 5% to 30% by weight, or from 10% to 25% by weight, or from 15% to 20% by weight.
In another embodiment, the polymer is present and may be a crosslinked aprotic polymer and/or a branched polymer, preferably of the type multi-branch. According to one embodiment, the polymer comprises at least one polymer segment chosen from polyether ionic conductive segments,

4 polythioether, polyester, polythioester, polycarbonate, polythiocarbonate, polyimide, polysulfonimide, polyamide, polysulfonamide, polyphosphazene, and THE
ionic non-conductive segments polyacrylate, polymethacrylate, polystyrene, polysiloxane, polyurethane, polyethylene, polypropylene, or a copolymer or combination of two or more of these.
According to another embodiment, the polymer comprises at least one segment polymer comprising a block copolymer with at least two units different repetitive in order to reduce the crystallinity of the crosslinked polymer, by example, the polymer segment comprising, before crosslinking, a copolymer with blocks comprising at least one solvating segment of alkali metal ion or alkaline earth and a crosslinkable segment comprising crosslinkable units.

According to one embodiment, the solvating segment of alkali metal ion or alkaline earth is chosen from homo- and copolymers comprising units repetitive Formula II:
-(CH2-CH-0)x-i R
Formula II
in which, R is chosen from H, Ci-Cioalkyl, and ¨(CH2-0-RaRb);
Ra is (CH2-CH2-0)y; And Rb is a Ci-Cioalkyl group.
In one embodiment, the crosslinkable units include functional groups chosen from acrylates, methacrylates, allyls, vinyls, hydroxides, epoxides, aldehydes, carboxylic acids, halophenyls, halobenzyls, alkynes, azides, amines, thiols and any combination thereof.
In certain embodiments, the polymer is present in the material composite at a concentration located in the range of 1% to 80% in weight, from 5% to 70% by weight, or 10% to 50% by weight, or from 20% to 40% by weight.

5 According to another embodiment, the inorganic particles comprise a inorganic compound of amorphous, ceramic or glass-ceramic type, by example, oxide, sulfide or oxysulfide. Preferably, the inorganic compound of amorphous type, ceramic or glass ceramic is an oxide. In another way embodiment, the inorganic particles comprise a ceramic chosen among A1203, Mg2B205, Na20=2B203, xMgO=yB203.zH20, TiO2, ZrO2, ZnO, Ti203, Si02, Cr203, Ce02, B203, B20, SrBi4Ti4015, LLTO, LLZO, LAGP, LATP, Fe203, BaTiO3, y-LiA102, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), sulphide ceramics (such as Li7P3S11), glass ceramics (such as LIPON, etc.), and other ceramics, as well as their combinations. Preferably, the ceramic is chosen from A1203, Mg2B205, Na20=2B203, xMg0=yB203.zli20, Ti02, Zr02, ZnO, Ti203, Si02, Cr203, Ce02, B203, B20, SrBi4Ti4015, LLTO, LLZO, LAGP, LATP, Fe203, BaTiO3, y-LiA102, sieve molecular and zeolites (e.g., aluminosilicate, silica mesoporous), glass ceramics (such as LIPON, etc.), as well as their combinations.
According to one embodiment, the inorganic particles are in the form of spherical particles, rods, needles, nanotubes, or one of their combinations.
According to one embodiment, the inorganic particles comprise a compound chosen from the compounds of formula Li1i-2AlzM2-z(PO4)3, where M is Ti, Ge or a combination of these, and 0 <z < 1, for example, z can be located In the interval from 0.1 to 0.9, or from 0.3 to 0.7, or from 0.2 to 0.4.
In another embodiment, which the inorganic particles comprise a compound chosen from the compounds of formulas Li7-xLa3Zr2Mxx012 and Li3yLa(2/3)-yTi1-y,MYy,03 in which Mx is chosen from Al, Ga, Ta, Fe, and Nb; MY is chosen from Ba, B, Al, Si and Ta; x is such that 0 É x É
1; there is such that 0 <y <0.67; and y' is such that 0 É y'< 1. For example, x can be locate in the interval from 0 to 0.5, where x is zero and Mx is absent.

6 According to one embodiment, the content of inorganic particles is located In the range of 1% to 95% by weight, or 5% to 90% by weight, or 5% to 80% by weight weight, or from 5% to 70% by weight, or from 5% to 60% by weight, or from 5% to 50% by weight, or from 5% to 40% by weight, or from 5% to 25% by weight, or from 5% to 15% by weight.
According to another embodiment, the composite material comprises the polymer and furthermore a plasticizing agent. For example, the plasticizing agent can be selected among glycol diether liquids (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and others similar. In one embodiment, the plasticizing agent may be present In the composite material at a concentration located in the range of 0.1% to 50%
by weight, or from 10% to 50% by weight, or from 20% to 40% by weight.
According to another embodiment, the composite material further comprises a salt. For example, the salt may include an alkali metal cation or alkaline-earth, preferably an alkali metal (preferably Li), and a chosen anion among hexafluorophosphate (PF6-), bis(trifluoromethanesulfonyl)imide anions (TFSI-), bis(fluorosulfonyl)imide (FSI-), (flurosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI)-), 2-trifluoromethyl1-4,5-dicyanoimidazolate (TDI-), 4,5-dicyano-1,2,3-triazolate (DCTA-), bis(pentafluoroethylsulfonyl)imide (BETI-), difluorophosphate (DFP-), tetrafluoroborate (BF4-), bis(oxalato)borate (BOB-), nitrate (NO3-), chloride (C1-), bromide (Br), fluoride (F), perchlorate (C104-), hexafluoroarsenate (AsF6-), trifluoromethanesulfonate (S03CF3-) (Tf), fluoroalkylphosphate [PF3(CF2CF3)3]
(FAP-), tetrakis(trifluoroacetoxy)borate [B(OCOCF3)4]- (TFAB-), bis(1,2-benzenediolato(2-)-0.0')borate [B(C602)2]- (BBB-), difluoro(oxalato)borate (BF2(C204) -) (FOB), an anion of formula BF204Rx" (Where Rx = C2-4a1ky1e), and moon of their combinations, for example LiTFSI or LiFSI.
According to a second aspect, the present document concerns a solid electrolyte comprising a layer of composite material as defined here.

7 According to a third aspect, the present technology relates to a cell electrochemical comprising a negative electrode, a positive electrode, and A
solid electrolyte, in which at least one of the positive electrode, the electrode negative and the electrolyte comprises a composite material as defined here.
According to a embodiment, the electrochemical cell comprises an electrode negative, a positive electrode, and a solid electrolyte, in which the electrolyte solid is as defined here. According to another embodiment, the solid electrolyte is as here defined and at least one of the negative electrode and the positive electrode includes a composite material as defined here.
According to one embodiment, the positive electrode comprises a material positive electrode possibly on a current collector, in which the positive electrode material comprises an electrochemically active material positive electrode. According to another embodiment, the material electrochemically active positive electrode is chosen from phosphates of metals, lithiated metal phosphates, metal oxides, and oxides of lithiated metals. According to yet another embodiment, the material electrochemically active positive electrode is LiM'PO4 where M' is Fe, Ni, Mn, Co, or a combination thereof, LiV308, V205F, LiV205, LiMn204, LiM"02, where M" is Mn, Co, Ni, or a combination thereof (such as NMC, LiMnxCoyNiz02 with x+y+z = 1), Li(NiMm)02 (where M" is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), sulfur, selenium or elemental iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, materials carbon-based active materials such as graphite, cathode active materials organic (such as polyimide, poly(2,2,6,6-tetramethylpiperidinyloxy-4-y1 methacrylate) (PTMA), tetralithium perylene-3,4,9,10-tetracarboxylate (PTCLi4), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), rr- dicarboxylates conjugates, and anthraquinone), or a combination of two or more of these materials when they are compatible with each other.

8 According to one embodiment, the electrochemically active material electrode positive is in the form of possibly coated particles (for example, of polymer, ceramic, carbon or a combination of two or more these).
According to another embodiment, the positive electrode material comprises in in addition to an electronic conductive material, for example, comprising at least one of carbon blacks (e.g. Ketjenblack TM or Super PTm), black acetylene (for example, Shawinigan black in Denka Tm black), graphite, graphene, carbon fibers or nanofibers (for example, carbon fibers formed in gas phase (VGCFs)), carbon nanotubes (e.g., single-walled (SWNT), multi-wall (MWNT)) or metal powders.
In some embodiments, the positive electrode material includes in in addition to a binder, for example, the binder is a polymer as defined below above, or a binder chosen from rubber type binders (such as SBR (rubber styrene-butadiene), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)), or binders fluoropolymer type (such as PVDF (polyvinylidene fluoride), PTFE
(polytetrafluoroethylene), and combinations thereof), optionally comprising A
additive like CMC (carboxymethylcellulose). According to other modes of embodiment, the positive electrode material further comprises a salt, inorganic particles of ceramic or glass type, or even others materials compatible active ingredients (e.g., sulfur), and/or the electrode material positive further comprises the composite material defined here.
In another embodiment, the negative electrode of the cell electrochemical comprises an electrochemically active electrode material negative.
According to one embodiment, the electrochemically active material electrode negative comprises a metallic film comprising an alkali or alkaline metal earthy. For example, the metal film comprises lithium comprising less of

9 1000 ppm (or less than 0.1% by mass) impurities. Alternatively, the film metal comprises an alloy of lithium and an element chosen from metals alkalis other than lithium (such as Na, K, Rb, and Cs), alkaline metals earthy (such such as Mg, Ca, Sr, and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, SM, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel and germanium (e.g. Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, TI, Ni, or Ge), preference, the alloy comprising at least 75% by mass of lithium, or between 85% and 99.9 %
in mass of lithium.
In another embodiment, the electrochemically active material negative electrode comprises an intermetallic compound (for example, SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2 and CoSn2), a metal oxide, a nitride of metal, a metal phosphide, a metal phosphate (for example, LiTi2(PO4)3), a metal halide (for example, a metal fluoride), a metal sulfide metal, a metal oxysulfide, a carbon (for example, graphite, graphene, the oxide of reduced graphene, a hard carbon, a soft carbon, exfoliated graphite and amorphous carbon), silicon (Si), a silicon-carbon composite (Si-C), a silicon oxide (Si0x), a silicon oxide-carbon composite (SiOx-C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnOx), a tin oxide-carbon composite (SnOx-C), and combinations thereof, when compatible. According to another embodiment, the metal oxide is chosen among the compounds of formulas M"b0c (where M" is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof; and b and c are numbers such that ratio c:b is in the range 2 to 3) (for example, Mo03, Mo02, MoS2, V205, and TiNb207), spinel oxides (for example, NiCo204, ZnCo204, MnCo204, CuCo204, and CoFe204) and LiM"m0 (where M" is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof) (for example, a titanate of lithium (such as Li4Ti5012) or a lithium molybdenum oxide (such as Li2Mo4013)).

In some embodiments, the electrochemically active material negative electrode is in the form of possibly coated particles (by example, polymer, ceramic, carbon or a combination of two or more of these).
In one embodiment, the negative electrode material comprises besides an electronic conductive material, for example, comprising at least one of carbon blacks (e.g. Ketjenblack TM or Super PTm), acetylene blacks (for example, Shawinigan black in DenkaTm black), graphite, graphene, fibers or carbon nanofibers (e.g., phase-formed carbon fibers gaseous (VGCFs)), carbon nanotubes (e.g. single-walled (SWNT), multi-wall (MWNT)) or metal powders.
In another embodiment, the negative electrode material comprises in in addition to a binder, for example, the binder is a polymer as defined below above, or a binder chosen from rubber type binders (such as SBR (rubber styrene-butadiene), NBR (acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), ACM (acrylate rubber)), or binders fluoropolymer type (such as PVDF (polyvinylidene fluoride), PTFE
(polytetrafluoroethylene), and combinations thereof), optionally comprising A
additive like CMC (carboxymethylcellulose).
According to yet another embodiment, the negative electrode material further comprises a salt, inorganic particles of ceramic type or glass, or other compatible active materials, and/or the composite material such as defined here.
According to a fourth aspect, the present technology relates to an accumulator electrochemical comprising at least one electrochemical cell such as here defined. According to one embodiment, the electrochemical accumulator is a lithium battery or a lithium-ion battery.

According to a fifth aspect, this document concerns the use of a electrochemical accumulator as defined here, in portable devices, by example cell phones, cameras, tablets or laptops, in electric or hybrid vehicles, or in the renewable energy storage.
According to a final aspect, the present technology also relates to a method of preparation of a composite material as defined here, comprising a step of mixture of inorganic particles, fluorinated compound, and optionally polymer. According to one embodiment, the mixing step comprises the polymer and optionally a crosslinking agent. According to another mode of realization, the mixing step comprises the polymer and the crosslinking agent and THE
The method further comprises a step of crosslinking the polymer.
BRIEF DESCRIPTION OF THE FIGURES
Figure 1 presents the infrared spectroscopy results of: (a) LATP;
(b) NMTFAm; (c) DAEDAm; (d) NMTFAm/LATP mixture; and (e) the mixture DAEDAm/LATP.
Figure 2 presents the solid-state NMR results: (a) 1H of NMTFAm and NMTFAm/LATP mixture; (b) 6Li of LATP; (c) 6Li of the NMTFAm/LATP mixture.
Figure 3 shows the Young's modulus of the membrane prepared in Example 1(d).
Figure 4 shows the ionic conductivity results as a function of temperature in (a) for Cells 1 to 6 and 8 to 15; and in (b) for the Cell 7 in comparison of a LATP powder.
Figure 5 shows the potential versus time for Cell 4 cycled to current densities ranging from C/3 to 5C.
Figure 6 shows the electrochemical stability results for the Cell carried out at voltages ranging from 3.5 V to 5 V.

Figure 7 shows the capacity and coulombic efficiency of an NMC/Li cell in function of the number of cycles according to Example 3(e)(i).
Figure 8 shows the galvanostatic charge and discharge curves at C/6 of an LFP/Li battery as a function of the number of cycles according to Example 3(e)(ii).
DETAILED DESCRIPTION
All technical and scientific terms and expressions used here have the even meaning than that generally understood by the person skilled in the art of the present technology. The definition of certain terms and expressions used is nevertheless provided below.
The term approximately as used herein means approximately, in the region of, and around. When the term approximately is used in connection with a numerical value, it modifies it, for example, above and below by a variation of 10% compared to the nominal value. This term can also take into account, for example, the experimental error of a device of measurement or rounding of a value.
When a range of values is mentioned in this application, the lower and upper limits of the interval are, unless otherwise indicated opposites, always included in the definition.
The chemical structures described here are drawn following the conventions of domain. Also, when an atom, such as a carbon atom, as drawn seems to include an incomplete valence, then we will assume that the valence is satisfied by one or more hydrogen atoms even if they are not explicitly drawn.
This document presents a composite material comprising particles inorganic compounds, a fluorinated amide and optionally a polymer. Preferably, fluorinated amide is a compound of Formula I:

H
Formula I
in which :
R1 and R2 are chosen independently at each occurrence from a optionally substituted linear or branched Ci-salkyl group, a C3- group optionally substituted 8cyc10a1ky1e, optionally C6aryl substituted, an optionally substituted C3-8heterocycloalkyl group, and a band optionally substituted C6-6heteroaryl;
X1 is selected from 0 and NH or X1 is absent;
wX2 is chosen from C(0), S(0)2, and Si(R3R4), where R3 and R4 are independently at each occurrence a linear or branched Cl-salkyl group optionally substituted, or X2 is absent;
in which at least one of R1, R2, R3 and R4 is a group substituted by one or more fluorine atom(s).
Some examples of compounds of Formula I include compounds in which :
- X1 is absent and X2 is chosen from C(0), S(0)2, and If(R3R4);
- X1 is chosen from 0 and NH and X2 is absent; Or - X1 and X2 are absent.
According to certain examples, R1 is a group substituted by one or more atom(s) fluorine, for example, a perfluorinated group. This group can be a group Below linear or branched salkyl, or a linear or branched C1-4alkyl group, or Again a Ci-2a1ky1e group.
The R2 group can be a group substituted by one or more atom(s) of fluorine, for example, a perfluorinated group. This group can be a group Below salkyl linear or branched, or a linear or branched C1-4a1ky1e group, or a group This-2a1ky1e. Alternatively, R2 may be a C3-8cyc10a1ky1e group possibly substituted, or an optionally substituted C3-6cyc10a1ky1e group, or a group C5-6cyc10a1ky1e optionally substituted.
Non-limiting examples of fluorinated compounds include N- compounds methyltrifluoroacetamide (NMTFAm), N-methylpentaproprionamide (NMPPPAm), N-cylcopentyltrifluoroacetam ide (NCPTFAm), N-trifluoromethylsulfonyl trifluoroacetam ide (NTFMSTFAm), N-trimethylsilyl trifluoroacetam ide (NTMSTFAm), and bistrifluoroacetamide (BTFAm).
The concentration of the compound in the composite material can be located, by for example, in the range of 1% to 90% by weight, or 1% to 70% by weight, or from 1% to 50% by weight, or from 1% to 40% by weight, or from 5% to 30% by weight, or from 10% to 25% by weight, or from 15% to 20% by weight.
The polymer, when present in the composite material, may comprise at least one polymer segment chosen from ionic conductive segments of polyether, polythioether, polyester, polythioester, polycarbonate type, polythiocarbonate, polyimide, polysulfonimide, polyamide, polysulfonamide, polyphosphazene, or among the non-conductive ionic polyacrylate segments, polymethacrylate, polystyrene, polysiloxane, polyurethane, polyethylene, polypropylene. The polymer can also be a copolymer comprising the units two or more of these segments or a combination of two or more of these this. The copolymer can be a random, statistical, alternating copolymer, with blocks, etc.
The polymer is preferably a crosslinked aprotic polymer and/or a polymer branched, preferably of the multi-branched type (star configuration, comb, etc.). By example, the polymer comprises at least one polymer segment comprising a block copolymer with at least two different repeating units in order to reduce the crystallinity of the crosslinked polymer. For example, the segment polymer can comprise, before crosslinking, a block copolymer comprising at least one solvating segment of alkali or alkaline earth metal ion and a segment crosslinkable comprising crosslinkable units. An example of a segment solvant of alkali or alkaline earth metal ion is chosen from homo- and copolymers comprising repeating units of Formula 11:
-(CH2-CH-0)x-i R
Formula II
in which, R is chosen from H, Ci-Cioalkyl, and ¨(CH2-0-RaRb);
Ra is (CH2-CH2-0)y; And Rb is a Ci-Cioalkyl group.
Non-limiting examples of crosslinkable units include groups functional elements chosen from acrylates, methacrylates, allyls, vinyls, hydroxides, epoxides, aldehydes, carboxylic acids, halophenyls, halobenzyls, alkynes, azides, amines, thiols and any combination thereof.
According to another example, the composite material comprises the crosslinked polymer, Or the crosslinkable group was converted into its crosslinked version.
The concentration of the polymer in the composite material can generally be be in the range of 1% to 80% by weight, 5% to 70% by weight, or 10%

at 50% by weight, or from 20% to 40% by weight.
The inorganic particles preferably comprise an inorganic compound of amorphous, ceramic or glass-ceramic type, for example, oxide, sulphide or oxysulfide, preferably an oxide. The inorganic compound can be driver ionic or not, preferably ionic conductor.
Non-limiting examples of inorganic compounds include Compounds OR ceramics A1203, Mg2B205, Na20=2B203, xMg0=yB203.zH20, Ti02, Zr02, ZnO, Ti203, SiO2, Cr203, Ce02, B203, B20, SrBi4Ti4015, LLTO, LLZO, LAGP, LATP, Fe203, BaTiO3, y-LiA102, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), sulphide ceramics (such as Li7P3S1 1), glass ceramics (such as LIPON, etc.), and other ceramics, as well that their combinations, preferably chosen from A1203, Mg2B205, Na20=2B203, xMg01/B203.zH20, Ti02, Zr02, ZnO, Ti203, Si02, Cr203, Ce02, B203, B20, SrBi4Ti.4015, LLTO, LLZO, LAGP, LATP, Fe203, BaTiO3, y-LiA102, sieve molecular and zeolites (e.g., aluminosilicate, silica mesoporous), glass ceramics (such as LIPON, etc.), as well as their combinations. THE
compound inorganic is preferably in the form of particles, the particles being able to be of varied shape, for example in the form of spherical particles, in sticks, in needles, nanotubes, or one of their combinations.
For example, the inorganic particles comprise a compound chosen from compounds of formula Li1i-zAlzM2-z(PO4)3, where M is Ti, Ge or a combination of these, and 0 < z < 1, for example, z can lie in the interval of 0.1 to 0.9, or from 0.3 to 0.7, or from 0.4 to 0.6, or from 0.2 to 0.5, or from 0.2 to 0.4.
According to other examples, the inorganic particles comprise a compound chosen from the compounds of formulas Li7-xLa3Zr2Mxx012 and Li3yLa(2/3)-y-ri1-y'MYy'03 in which Mx is chosen from Al, Ga, Ta, Fe, and Nb; MY is chosen from Ba, B, Al, Si and Ta; x is such that 0 É x É 1; y is such that 0 <y <0.67; and there it is such as 0 5 y'< 1, preferably x is in the range 0 to 0.5, or x is zero and Mx is absent, preferably y' is in the range 0 to 0.5, or y' is 0 and MY
is absent.
The content of inorganic particles in the composite material can be located in the range of 1% to 95% by weight, or 5% to 90% by weight, or 5% to 80% by weight, or from 5% to 70% by weight, or from 5% to 60% by weight, or from 5% to 50% by weight, or from 5% to 40% by weight, or from 5% to 25% by weight, or from 5% to 15% by weight.
According to certain examples, the composite material comprises the polymer and a agent plasticizer. Non-limiting examples of plasticizing agents include glycol diether liquids (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and others similar.
When he is present, the concentration of plasticizer in the composite material can be in the range of 0.1% to 50% by weight, or from 10% to 50% by weight, Or from 20% to 40% by weight.
According to a preferred example, the composite material further comprises a salt of lithium, for example, a salt comprising a cation of an alkali metal or alkaline-earth, preferably an alkali metal (preferably Li), and an anion. Of the non-limiting examples of anions include hexafluorophosphate anions (PF6-), bis(trifluoromethanesulfonyl)imide (TES I), bis(fluorosulfonyl)imide (FS I), (flurosulfonyl)(trifluoromethanesulfonyl)imide ((FSI)(TFSI)-), 2-trifluoromethyl1-4,5-dicyanoimidazolate (TOP), 4,5-dicyano-1,2,3-triazolate (DCTA-), bis(pentafluoroethylsulfonyl)imide (BETI-), difluorophosphate (DFP-), tetrafluoroborate (BF4-), bis(oxalato)borate (BOB-), nitrate (NO3-), chloride (See), bromide (Br), fluoride (F-), perchlorate (C104-), hexafluoroarsenate (A5F6-), trifluoromethanesulfonate (S03CF3-) (Tf), fluoroalkylphosphate [PF3(CF2CF3)3]
(FAP-), tetrakis(trifluoroacetoxy)borate [B(OCOCF3)4]- (TFAB-), bis(1,2-benzenediolato(2-)-0.0')borate [B(C602)2]- (BBB-), difluoro(oxalato)borate (BF2(C204) -) (FOB), an anion of formula BF204Rx- (where Rx = C2-4a1ky1e), and moon of their combinations, for example LiTFSI or LiFSI.
The present composite material is prepared according to a process comprising at minus one step of mixing the inorganic particles, the fluorinated compound, and possibly polymer and other optional elements such as here described.
The mixing step of the process can therefore include the polymer and possibly a crosslinking agent. The mixing step of such a process can SO
be followed by a crosslinking step.
The composite material can be used in the composition of a layer electrolyte solid or electrode material.
For example, the electrolyte comprises the composite material as defined here in a solid layer. This layer can be formed by mixing, in any what order, inorganic particles, electrolyte polymer or a precursor thereof, the fluorinated amide, and optionally a solvent, the plasticizer and or of a salt, and spreading the mixture on a support. The support can be temporary (such as stainless steel support, polypropylene, etc.) and be removed Before assembly with the rest of the electrochemical cell. The support can Also be the surface of an electrode material, which will have been prepared prior.
When a polymer precursor is used, the spread layer is treated in order to to polymerize or cross-link the polymer, for example, by treatment thermal, by irradiation (such as UV, microwave, gamma rays, beam of electrons), or a combination of the two, possibly in the presence of a initiator. When a solvent is present, the material is preferably dried, by example, before crosslinking or assembling with the other components of the cell electrochemical.
The present composite material is present in an electrochemical cell In at least one of the electrolyte, the positive electrode or the negative electrode, preferably in the electrolyte layer.
The positive electrode material generally comprises a material electrochemically active and can be self-supporting or applied to a current collector. The electrochemically active electrode material positive can, among others, be chosen from metal phosphates, phosphates of lithiated metals, metal oxides, and lithiated metal oxides.
Examples of electrochemically active materials include LiM'PO4 where M' is Fe, Ni, Mn, Co, or a combination thereof, LiV308, V205F, LiV205, LiMn204, LiM"02, where M" is Mn, Co, Ni, or a combination thereof (such as THE
NMC, LiMnxCoyNiz02 with x+y+z = 1), Li(NiMm)02 (where M" is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), sulfur, selenium or iodine elemental, iron(III) fluoride, copper('I) fluoride, iodide lithium, carbon-based active materials such as graphite, active materials organic cathode (such as polyimide, poly(2,2,6,6-tetramethylpiperidinyloxy-4-y1 methacrylate) (PTMA), perylene-3,4,9,10-tetra-lithium tetracarboxylate (PTCLi4), naphthalene-1,4,5,8- dianhydride tetracarboxylic acid (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), -rr-conjugated dicarboxylates, and anthraquinone), or a combination of two or more of these materials when they are compatible with each other.
The positive electrode electrochemically active material is preferably below form of possibly coated particles (for example, of polymer, of ceramic, carbon or a combination of two or more of these).
The electrode material may further include a conductive material electronic, for example, comprising at least one of the carbon blacks (for example example, Ketjenblack TM or Super Pn"), acetylene blacks (e.g., black Shawinigan in black DenkaTm), graphite, graphene, fibers or nanofibers carbon (e.g. gas-formed carbon fibers (VGCFs)), carbon nanotubes (e.g., single-walled (SWNT), multi-walled (MWNT)) or metal powders.
The electrode material can be prepared in the same way as the layer of electrolyte, except that the medium for spreading may be the surface a layer of solid electrolyte or a current collector.
When the positive electrode material does not include the material composite, this can include the electrochemically active material such as here defined, a binder and possibly an electronic conductive material and/or a salt such that here defined.
Non-limiting examples of electrode material binders include polymers described above in connection with the composite material, but also rubber-like binders (such as SBR (styrene-butadiene rubber), NBR
(acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (acrylonitrile-butadiene rubber), epichlorohydrin), ACM (acrylate rubber)), or binders of the type fluoropolymers (such as PVDF (polyvinylidene fluoride), PTFE

(polytetrafluoroethylene), and combinations thereof). Certain binders, such as those of rubber type, can also include an additive such as CMC
(carboxymethylcellulose).
Other additives may also be present in the electrode material positive, such as inorganic particles of ceramic or glass type, or even other compatible active materials (e.g., sulfur).
The negative electrode includes an electrochemically active material electrode negative which can be formed from a metallic film, for example, comprising a alkali or alkaline earth metal. According to one example, the metallic film is constituted of lithium comprising less than 1000 ppm (or less than 0.1% by mass) impurities. Alternatively, the metal film comprises an alloy of lithium and an element chosen from alkali metals other than lithium (such that Na, K, Rb, and Cs), alkaline earth metals (such as Mg, Ca, Sr, and Ba), metals land rare (such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Read), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel and germanium (e.g. Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, TI, Ni, or Ge). The alloy may comprise at least 75%
in mass of lithium, or between 85% and 99.9% by mass of lithium.
Other examples of electrochemically active negative electrode material include an intermetallic compound (for example, SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2 and CoSn2), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (for example, LiTi2(PO4)3), a metal halide (for example, a metal fluoride), a metal sulfide, A
metal oxysulfide, a carbon (e.g. graphite, graphene, the oxide of reduced graphene, hard carbon, soft carbon, exfoliated graphite and carbon amorphous), silicon (Si), a silicon-carbon composite (Si-C), an oxide of silicon (Si0x), silicon oxide-carbon composite (SiOx-C), tin (Sn), a tin-carbon composite (Sn-C), a tin oxide (SnOx), an oxide composite tin-carbon (SnOx-C), and their combinations, when compatible. By example, the metal oxide can be chosen from the compounds of formulas M"b0c (where M" is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof this;
and b and c are numbers such that the ratio c:b lies in the interval ranging from 2 to 3) (for example, M003, M002, MoS2, V205, and TiNb207), spinel oxides (e.g., NiCo204, ZnCo204, MnCo204, CuCo204, and CoPe204) and LiM
............ 0 (where M
.................................................. .............................
is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof) (for example, a lithium titanate (such as Li4Ti5012) or a lithium oxide lithium and molybdenum (such as Li2Mo4013)).
When the negative electrode is not in the form of a metal film, it rather comprises particles of an electrochemically active material negative electrode possibly coated (for example, with polymer, ceramic, carbon or a combination of two or more of these). THE
negative electrode material may also include other components such than those described for the negative electrode (such as a conductive material electronics, the present composite material, a salt, a binder, particles inorganic ceramic or glass type, or other active materials compatible).
This document concerns an electrochemical accumulator comprising at least less an electrochemical cell as defined here. For example, the accumulator electrochemical is a lithium or lithium-ion battery.
According to another aspect, the electrochemical accumulators of the present application are intended for use in portable devices, e.g.
cell phones, cameras, tablets or computers portable, in electric or hybrid vehicles, or in storage of renewable energy.

EXAMPLES
The following examples are for illustrative purposes and should not be used interpreted as limiting the scope of the invention as described.
Unless otherwise indicated, numbers expressing quantities of components, preparatory conditions, concentrations, properties, etc.
used here should be interpreted as modified in each instance by the term approximately . At the very least, each numerical parameter should be interpreted in light of the number of significant figures reported and by the application of usual rounding techniques. So unless otherwise noted, THE
numerical parameters mentioned here are approximations which can vary depending on the properties sought. However, although the parameters defining the broadest modes of realization are approximations, the numerical values presented in the following examples are reported THE
more precisely possible. However, any numerical value contains inherent margin of error resulting from variations in experiments, measurements, statistical analyses, etc.
The crosslinkable polymers used in the examples which follow are polyethers comprising crosslinkable units, as described in the patent US No. 7,897,674 (referred to below as polymer US'674, which is a branched polymer of multi-branched type comprising units crosslinkable) or in American patent N 6,903,174 (designated below like the polymer US'174, which is linear and includes groups crosslinkable pendants).
Example 1 ¨ Preparation of electrolytes (a) Polymer electrolyte (Comparative) 2 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), 8 g of polymer US'674 and 0.08g of Irgacuremc are mixed in a vial at temperature ambient. Once a homogeneous solution is obtained, coating the solution on a thin stainless steel sheet is made. After UV irradiation under nitrogen for 3 minutes, the solid polymer electrolyte membrane is thus obtained.
(b) Composite electrolyte with HNT and DAEDAm (Comparison) 0.5g LiTFSI, 0.77g tetraethylene glycol dimethyl ether (TEGDME), 0.25g N,N=diacetylethylenediamine (DAEDAm) and 0.24g of Halloysite nanotubes (HNT) are mixed well in a flask at room temperature. Once a homogeneous dispersion obtained, 0.75g of US'674 polymer and 0.01g of Irgacuremc are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin sheet of stainless steel. The membrane electrolyte composite thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
(c) Composite electrolyte with HNT and NMTFAm 0.5g LiTFSI, 0.69g TEGDME, 0.44g N-methyltrifluoroacetamide (NMTFAm) and 0.26g of HNT are mixed well in a flask at temperature ambient. Once a homogeneous dispersion is obtained, 0.67g of US'674 polymer and 0.01g of Irgacuremc are added. After 1 hour of stirring at temperature ambient, the dispersion is coated on a thin stainless steel sheet.
There composite electrolyte membrane thus obtained is hardened by UV irradiation below nitrogen for 3 minutes.
(d) Composite electrolyte with LATP and NMTFAm 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of NMTFAm and 0.26g of Li1.3A10.3Ti1.7(PO4)3 (LATP) are mixed well in a flask at the temperature ambient. Once a homogeneous dispersion is obtained, 0.67g of US'674 polymer and 0.01g of Irgacuremc are added. After 1 hour of stirring at temperature ambient, the dispersion is coated on a thin stainless steel sheet.
There composite electrolyte membrane thus obtained is hardened by UV irradiation below nitrogen for 3 minutes.
(e) Composite electrolyte with LATP and DAEDAm (Comparison) 0.5g of LiTFSI, 0.77g of TEGDME, 0.25g of DAEDAm and 0.24g of LATP are mixed well in a flask at room temperature. Once a dispersion homogeneous obtained, 0.75g of polymer US'674 and 0.01g of Irgacuremc are added.

After 1 hour of stirring at room temperature, the dispersion is coated on a thin sheet of stainless steel. The composite electrolyte membrane Thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
(t) Polymer electrolyte with NMTFAm (Comparison) 0.5g of LiTFSI, 0.77g of TEGDME, and 0.25g of NMTFAm are mixed well in a vial at room temperature. Once a homogeneous solution obtained, 0.99g of US'674 polymer and 0.01g of Irgacuremc are added. After 1 hour of stirring at room temperature, the solution is coated on a leaf thin stainless steel. The polymer electrolyte membrane thus obtained East cured by UV irradiation under nitrogen for 3 minutes.
(g) Ceramic electrolyte with LATP and NMTFAm 0.35g of LATP and 0.15g of NMTFAm are mixed well and ground in a mortar at room temperature. Then the powder is compressed into pellet round at a pressure of 120 psi with a diameter of 16mm and a thickness of 420pm. A comparative sample with the pure LATP powder was also prepared in the same way.
(h) Composite electrolyte with LLZO and NMTFAm 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of NMTFAm and 0.26g of Li7La3Zr2012 (LLZO) are mixed well in a flask at room temperature. Once a homogeneous dispersion obtained, 0.67g of US'674 polymer and 0.01g of Irgacuremc are added. After 1 hour of stirring at temperature ambient, the dispersion is coated on a thin stainless steel sheet. The membrane of composite electrolyte thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
(i) Composite electrolyte with LATP, NMTFAm and US'174 polymer 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of NMTFAm and 0.26g of LATP are mixed well in a flask at room temperature. Once a dispersion homogeneous obtained, 0.67g of polymer US'174 and 0.01g of Irgacuremc are added.

After 1 hour of stirring at room temperature, the dispersion is coated on a thin sheet of stainless steel. The composite electrolyte membrane Thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
(I) Composite electrolyte with LATP and NMPPPAm 0.5g LiTFSI, 0.77g TEGDME, 0.44g N-methylpentaproprionamide (NMPPPAm) and 0.26g of LATP are mixed well in a flask at temperature ambient. Once a homogeneous dispersion is obtained, 0.67g of US'674 polymer and 0.01g of Irgacuremc are added. After 1 hour of stirring at temperature ambient, the dispersion is coated on a thin stainless steel sheet.
There composite electrolyte membrane thus obtained is hardened by UV irradiation below nitrogen for 3 minutes.
(k) Composite electrolyte with LATP and NCPTFAm 0.5g LiTFSI, 0.77g TEGDME, 0.44g N-cylcopentyltrifluoroacetamide (NCPTFAm) and 0.26g of LATP are mixed well in a flask at temperature ambient. Once a homogeneous dispersion is obtained, 0.67g of US'674 polymer and 0.01g of Irgacuremc are added. After 1 hour of stirring at temperature ambient, the dispersion is coated on a thin stainless steel sheet.
There composite electrolyte membrane thus obtained is hardened by UV irradiation below nitrogen for 3 minutes.
(I) Composite electrolyte with LATP and NTFMSTFAm 0.5g LiTFSI, 0.77g TEGDME, 0.44g N-trifluoromethylsulfonyl trifluoroacetamide (NTFMSTFAm) and 0.26g of LATP are mixed well in a vial at room temperature. Once a homogeneous dispersion has been obtained, 0.67g of US'674 polymer and 0.01g of Irgacuremc are added. After 1 hour agitation at room temperature, the dispersion is coated on a thin sheet in steel stainless. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
(m)Composite electrolyte with LATP and NTMSTFAm 0.5g LiTFSI, 0.77g TEGDME, 0.44g N-trimethylsilyl trifluoroacetamide (NTMSTFAm) and 0.26g of LATP are mixed well in a flask at the ambient temperature. Once a homogeneous dispersion has been obtained, 0.67g of polymer US'674 and 0.01g of Irgacuremc are added. After 1 hour of stirring to the room temperature, the dispersion is coated on a thin steel sheet stainless. The composite electrolyte membrane thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
(n) Composite electrolyte with LATP and BTFAm 0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of bistrifluoroacetamide (BTFAm) and 0.26g of LATP is mixed well in a flask at room temperature. A

times a homogeneous dispersion obtained, 0.67g of US'674 polymer and 0.01g of Irgacuremc are added. After 1 hour of stirring at temperature ambient, the dispersion is coated on a thin stainless steel sheet. The membrane of composite electrolyte thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
(o) Composite electrolyte with LATP and less NMTFAm 0.5g LiTFSI, 0.65g TEGDME, 0.37g bis(trifluoromethanesulfonyl)imide of 1,1'-hexamethylene bis(1-methylpyrrolidinium), 0.11g of NMTFAm and 0.26g of The ATP are mixed well in a flask at room temperature. Once a homogeneous dispersion obtained, 0.60g of US'674 polymer and 0.01g of Irgacuremc are added. After 1 hour of stirring at room temperature, the dispersion is coated on a thin sheet of stainless steel. The membrane electrolyte composite thus obtained is hardened by UV irradiation under nitrogen for 3 minutes.
Example 2 ¨ Physico-chemical properties (a) Infrared spectroscopy of the particle-amide mixture In order to better understand the effect of the presence of fluorinated amide, analyzes chemicals were carried out. Infrared spectroscopy was carried out at the state solid on an Agilent-Cary 630 FTIR spectrometer. Particle-mixtures amide were prepared with a weight ratio 1.7/1 for NMTFAm/LATP and a weight ratio 1/1 for DAEDAm/LATP by grinding in a mortar. THE
infrared spectra of LATP, NMTFAm, DAEDAm and mixtures LATP/NMTFAm and LATP/DAEDAm are shown in Figures 1(a) to (e).
Figure 1(d) shows that a new signal appeared around 3550 cm-1 for the LATP/NMTFAm mixture, this being absent in the case of LATP/DAEDAm at Figure 1(e). This new signal indicates that there is an interaction between amide fluorinated and LATP ceramic, this interaction not being present in the case of non-fluorinated amide DAEDAm.
(b) NMR chemical structure of the NMTFAm/LATP mixture In order to confirm the results observed by infrared spectroscopy, the analyzes Solid NMR of NMTFAm and the NMTFAm/LATP mixture were carried out on a 500 MHz NMR spectrometer equipped with a 4 mm triple resonance probe with MAS (magic angle spinning), up to 15 kHz. Preparing the mixture NMTFAm/LATP is the same as described in 2(a). 1H and 6Li NMR spectra NMTFAm, LATP and the NMTFAm/LATP mixture are shown in Figures 2(a) to (c).

Figure 2(a) shows that the signals of NMTFAm are broader than those of NMTFAm/LATP mixture, indicating an interaction between NMTFAm and LATP
which significantly reduces the restriction of molecular mobility in THE
NMTFAm. In addition, a shift in the peak corresponding to the NH protons of NMTFAm towards higher frequency may indicate that more NH protons in the mixture are involved in hydrogen bonds.
Figure 2(c) shows that an additional signal at 1.2 ppm appeared in the 6Li NMR spectrum of the mixture after 1 day of storage compared to Figure 2(b), indicating that new Li + ions were generated by the interaction between the NMTFAm and LATP.
(c) Young’s modulus of the membrane The Young's modulus was evaluated for the membrane prepared in Example 1(d) on a TA Discovery DMA850 at 20 C. The film size for the measurement is

10.7 mm x 5.3 mm x 0.167 mm (length x width x thickness). The Rate procedure Control Strain Ramp was used. Figure 3 shows a graph of the module de Young of the membrane prepared in Example 1(d).
(d) Diffusion coefficient The ionic diffusion coefficient of the different elements of the membrane prepared in Example 1(d) was evaluated by gradient solid state NMR spectroscopy pulsed field of cores 1H, 7Li, and 19F. The NMR experiments were carried out on a 500 MHz NMR spectrometer equipped with a Diff50mc probe and inserts Double resonance RF 7Li-19F and 1H-19F.
The measurements were carried out at 25 C and 50 C. The gradient pulse is located in the range of 0.6 to 2.0 ms and the diffusion time was within the interval 40 to 100 ms depending on the kernel. The gradient strength was varied in 16 steps of 100 G/cm to 2500 G/cm.

Diffusion measures were accompanied by T2 relationship experiences using a CPMG pulse sequence with echo delay of 0.06 to 0.6 ms.
Up to 64 echoes were collected per experiment. The results are presented in Table 1.
Table 1. Diffusion coefficients measured by NMR spectroscopy NMTFAm Polymer NMTFAm TFSI- Li Li in*
Temp. LATP
(mes) lii (neis) 19F (naves) (naves) (mes) 50 C 3.1 x10-13 3.8x1 0-11 3.7x1 0-11 1.7x1 0-11 1.1x10-11 5.7x1 0-12 25 C 5.7)(10-14 1.4x1 0-11 1.4x1 0-11 6.6x10-12 4.7x10-12 2.9x10-12 Most species were very mobile in the sample, which permit to obtain a higher resolution of the NMR spectra.
The diffusion coefficients of NMTFAm measured from 1H and 19F NMR
match each other perfectly.
The diffusion coefficients of Li in LATP at 25 and 50 C correspond to values obtained with other samples containing LATP. This observation confirms that the diffusion of lithium in LATP is not dependent on LATP particles surrounded by polymer, especially considering that the mean square displacement of the species during the NMR experiment is about 0.5 to 1 pm (much smaller than the particle size of LATP
Who is about 10 pm).
Example 3 ¨ Electrochemical properties (a) Assembly of cells (symmetrical batteries) Symmetrical Li/Electrolyte/Li type button cells for measuring density critical current (CCD) and stainless steel/electrolyte/stainless steel type for measuring ionic conductivity were assembled. Membrane discs electrolyte polymer were cut with a diameter of 16 mm (for measuring ionic conductivity) or a diameter of 14mm (for CCD measurement) and tight between two electrodes. The configuration of each cell is presented as follows:
- Cell 1: Electrode/Example 1(a)/Electrode - Cell 2: Electrode/Example 1(b)/Electrode - Cell 3: Electrode/Example 1(c)/Electrode - Cell 4: Electrode/Example 1(d)/Electrode - Cell 5: Electrode/Example 1(e)/Electrode - Cell 6: Electrode/Example 1(f)/Electrode - Cell 7: Electrode/Example 1(g)/Electrode - Cell 8: Electrode/Example 1(h)/Electrode - Cell 9: Electrode/Example 1(i)/Electrode - Cell 10: Electrode/Example 1(j)/Electrode - Cell 11: Electrode/Example 1(k)/Electrode - Cell 12: Electrode/Example 1(I)/Electrode - Cell 13: Electrode/Example 1(m)/Electrode - Cell 14: Electrode/Example 1(n)/Electrode - Cell 15: Electrode/Example 1(o)/Electrode Electrode = Lithium metal or stainless steel (b) Ionic conductivity Electrochemical impedance spectroscopy was carried out with a system of Bio-logic VMP-300 at an amplitude of 100 mV and the frequency range of 1MHz to 200mHz.
Figures 4(a) and 4(b) show the ionic conductivity results for THE
Cells 1 to 15. The conductivity results at 50 C and 25 C are also presented in Table 2 below.
We see, for example, that the ionic conductivity in the electrolyte LATP/amide fluorinated (NMTFAm, 3.62 x 10-4 S/cm) at 20 C is much higher than that of LATP/non-fluorinated amide (DAEDAm, 9.29 x 10-5 S/cm) and Halloysite nanotubes/NMTFAm (2.64 x 10-5 S/cm). The ionic conductivity at 20 C is also generally higher for all electrolytes comprising a fluorinated amide in comparison to the electrolyte without fluorinated amide.
(c) Critical current density The critical current density was evaluated using a Bio-system.
logic VMP-3. The test begins at a current density of C/24 (1C = 3.0 mA/cm2), in gradually increasing it. The same current density was applied for charge and discharge the battery.
Figure 5 shows that Cell 4, a symmetrical Li/electrolyte/Li cell with the LATP/NMTFAm electrolyte of Example 1(d), is stable up to 5C (1C = 3.0 mA/cm2) at 25 C. The results are also summarized in Table 2 below.
Table 2. Electrolyte composition (wt%) and results from Cells 1 at 15 CCD conductivity LiTFSI Polymera TEGDME Ceramic Additive (x10 S/cm) .
#
has ( /0) (%) (%) (%) (%) at 25 C

1.35 0.163 C/6 DAEDAm HNT 4'66 1.14 C/3 3 20 26 27 NMTFAm HNT 0'842 0.264 1C

NMTFAm LATP 9'08 3.62 5C

DAEDAm LATP 4'0 0'929 C/3 6 20 36 27 NMTFAm 0 2.1 1.1 C/2 NMTFAm LATP 81 0.32 NMb NMTFAm LLZO 7'8 4.01 NMb NMTFAm LATP 4'93 3.04 C/12 NMPPPAm LATP 1'02 0.801 C/2

11 20 26 27 NCPTFAm LATP 4'54 2.61 1C

12 20 26 27 NTFMSTFAm LATP 8'8 4.15 C/2

13 20 26 27 8.01 3.67 C/2 NTMSTFAm LATP

14 20 26 27 BTFAm LATP 8.3 3.3 C/2 NMTFAm LATP 9.78 4.13 1C
has. Polymer US'674 with the exception of Cell 9, where polymer US'174 was used.
b. NM: not measured vs. The electrolyte also comprises 15% by weight of 1,1'-bis(trifluoromethanesulfonyl)imide hexamethylene bis(1-methylpyrrolidinium).

(d) Electrochemical stability In order to evaluate the electrochemical stability of the membrane prepared The example 1(d), a solution with 20% by weight of carbon black (Ketjenblack TM) has summer prepared.
0.5g of LiTFSI, 0.77g of TEGDME, 0.44g of NMTFAm and 0.26g of Li1.3A10.3Ti1.7(PO4)3 (LATP) were mixed well in a flask temperature ambient. Once a homogeneous dispersion has been obtained, 0.67g of US'674 polymer, 0.01g of azobisisobutyronitrile and a dispersion of 0.528g of black carbon in 6 mL of acetonitrile were added. After 1 hour of stirring at temperature ambient with a planetary centrifugal mixer, the dispersion was coated on a sheet of aluminum coated with conductive carbon. The solvent has Next was evaporated under vacuum at 40 C, then the membrane was placed in an oven at 100 under nitrogen for 10 min. On the carbon membrane, a layer of the electrolyte of Example 1(a) or Example 1(d) is coated. Layer of electrolyte is hardened by UV irradiation under nitrogen for 3 minutes. There complete membrane for measuring electrochemical stability is thus obtained.
For mounting button cells, membrane discs with a diameter of 16mm was cut off. The electrolyte side is covered with a sheet of lithium. The cells thus formed are named Cell 8 and Cell 9.
including respectively the membranes of Examples 1(a) and 1(d).

Electrochemical stability was assessed using a Bio-logic system VMP-3. The voltage varied from 3.5 V to 5 V with a rate of increase of 0.1 V
every 2 hours.
Figure 6 shows the electrochemical stability for Cell 9, including there membrane prepared in Example 1(d), and for Cell 8, comprising the membrane prepared in Example 1(a).
In summary, we can observe that the addition of N-methyltrifluoroacetamide (NMTFAm) in a composite electrolyte based on US'674 polymer and LATP (a phosphate type oxide ceramic) can greatly improve the conductivity ionic and stability at the Li/electrolyte interface (see Figure 1) at 25 C, stability oxidation of up to 4.5V. This observation is confirmed by the Ionic conductivity and critical current density (CCD) in cells symmetrical including electrolytes in comparison to other ceramics or amide.
(e) Assembly and performance of complete batteries Complete batteries using the electrolyte of Example 1(d) were assembled and their performance was evaluated.
(i) NMC811 battery/electrolyte/Li A cathode was prepared as described in the patent application PCT/CA2022/050159 including 73.2% by weight of active material oxide lithium manganese cobalt nickel (NMC811), which gives a charging rate approximately 8 mg/cm2. The electrolyte dispersion Example 1(d) was directly coated on the cathode and cured by UV irradiation under nitrogen for 3 minutes.
The electrolyte thickness is approximately 40 pm. A sheet of lithium metallic with a thickness of 50pm was used as an anode. A button battery 3.8cm2 was therefore assembled to evaluate the performance.

The performance evaluation was carried out on a Bio-Logic BCS-810 system with a voltage 2.75 ¨ 4.2 V and a charge-discharge speed C/6 ¨ 1C (1C =
1.2 mA/cm2) at 45 C. The battery capacity is around 4.4 mAh (1.2 mAh/cm2).
Figure 7 shows the cell capacity and coulombic efficiency as a function of number of cycles.
(ii) LFP/electrolyte/Li battery A LiFePO4 (LFP) cathode was prepared as in Example 3(e)(i) in replacing NMC811 with LFP as active ingredient at a concentration by weight of 70%, which gives a loading rate of approximately 12 mg/cm2. There dispersion of electrolyte Example 1(d) was directly coated on the cathode and hardened by UV irradiation under nitrogen for 3 minutes. The electrolyte thickness is about 40 p.m. A sheet of lithium metal with a thickness of 40 pm has was used as the anode. A 3.8 cm2 button cell battery was assembled to evaluate performance.
The performance evaluation was carried out on a Bio-Logic BCS-810 system with a voltage 2 ¨3.8 V and a charge-discharge speed C/6 ¨C/6 (1C = 1.2 mA/cm2) at 45 C. Battery capacity is approximately 3 mAh (0.8 mAh/cm2).
Figure 8 shows the galvanostatic charge and discharge curves at one charging and discharging speed of C/6.
Several modifications could be made to either mode of embodiment described above without departing from the scope of the present invention such than envisaged. References, patents or scientific literature documents referred to in this application are incorporated herein by reference in their entirety and for all purposes.

Claims (69)

1. Composite material comprising inorganic particles, a compound fluorinated, and optionally a polymer, in which the fluorinated compound is Formula l:
in which :
R1 and R2 are chosen independently at each occurrence from a linear or branched C1-8a1ky1e group optionally substituted, a C3- group optionally substituted 8cyc10a1ky1e, optionally C6aryl substituted, an optionally substituted C3-8heterocycl10a1ky1e group, and a band optionally substituted C6-6heteroaryl;
X1 is selected from 0 and NH or X1 is absent;
X2 is chosen from C(0), S(0)2, and Si(R3R4), where R3 and R4 are independently at each occurrence a linear or branched Cl-salkyl group optionally substituted, or X2 is absent;
in which at least one of R1, R2, R3 and R4 is a group substituted by one or more fluorine atom(s). 2. Composite material of claim 1, in which XI is absent and is chosen from C(0), S(0)2, and Si(R3R4). 3. Composite material of claim 1, in which X1 is chosen among 0 and NH and X2 is absent. 4. Composite material of claim 1, in which XI and X2 are absent. 5. Composite material of any one of claims 1 to 4, in which R1 is a group substituted by one or more fluorine atom(s). 6. Composite material of claim 5, in which R1 is a group perfluorinated. 7. Composite material of any one of claims 1 to 6, in which R1 is a linear or branched Cl-salkyl group, or a Ci- group aalkyl linear or branched, or a C1-2a1ky1e group. 8. Composite material of any one of claims 1 to 7, in which R2 is a group substituted by one or more fluorine atom(s). 9. Composite material of claim 8, in which R2 is a group perfluorinated. 10. Composite material of any one of claims 1 to 9, in in which R2 is a linear or branched C1-8a1ky1e group, or a C1- group aalkyl linear or branched, or a C1-2a1ky1e group. 11. Composite material of any one of claims 1 to 9, in in which R2 is an optionally substituted C3-8cyc10a1ky1e group, or a group Optionally substituted C3-6cyc10a1ky1e, or a C5-6cyc10a1ky1e group possibly substituted. 12. Composite material of any one of claims 1 to 9, in in which the compound is chosen from N-methyltrifluoroacetamide compounds (NMTFAm), N-methylpentaproprionamide (NMPPPAm), N-cylcopentyltrifluoroacetamide (NCPTFAm), N-trifluoromethylsulfonyl trifluoroacetamide (NTFMSTFAm), N-trimethylsilyl trifluoroacetamide (NTMSTFAm), and bistrifluoroacetamide (BTFAm). 13. Composite material of any one of claims 1 to 12, in in which the concentration of the compound in the composite material is within the range of 1% to 90% by weight, or 1% to 70% by weight, or 1% to 50% by weight weight, or from 1% to 40% by weight, or from 5% to 30% by weight, or from 10% to 25% by weight, or from 15% to 20% by weight. 14. Composite material of any one of claims 1 to 13, in which the polymer is present. 15. Composite material of claim 14, in which the polymer is A
crosslinked aprotic polymer. 16. Composite material of claim 14 or 15, in which the polymer is a branched polymer, preferably of the multibranched type. 17. Composite material of any one of claims 14 to 16, in which the polymer comprises at least one polymer segment chosen from polyether, polythioether, polyester ionic conductive segments, polythioester, polycarbonate, polythiocarbonate, polyimide, polysulfonimide, polyamide, polysulfonamide, polyphosphazene, and ionic nonconductor segments polyacrylate, polymethacrylate, polystyrene, polysiloxane, polyurethane, polyethylene, polypropylene, or a copolymer or combination of two or more of these. 18. Composite material of any one of claims 14 to 17, in which the polymer comprises at least one polymer segment comprising a block copolymer with at least two different repeating units in order to reduce the crystallinity of the crosslinked polymer. 19. Composite material of claim 18, in which the segment polymer comprises, before crosslinking, a block copolymer comprising at minus one alkali or alkaline earth metal ion solvate segment and one crosslinkable segment comprising crosslinkable units. 20. Composite material of claim 19, in which the segment alkali or alkaline earth metal ion solvant is chosen from homo-And copolymers comprising repeating units of Formula II:

in which, R is chosen from H, Ci-Cioalkyl, and ¨(CH2-0-RaRb);
Ra is (CH2-CH2-0)y; And Rb is a Ci-Cioalkyl group. 21. Composite material of claim 19 or 20, in which the units crosslinkable comprise functional groups chosen from among the acrylates, methacrylates, allyls, vinyls, hydroxides, epoxides, aldehydes, carboxylic acids, halophenyls, halobenzyls, alkynes, azides, amines, thiols and one of their combinations. 22. Composite material of any one of claims 14 to 21, in in which the polymer is present in the composite material at a concentration located in the range of 1% to 80% by weight, 5% to 70% by weight, or 10%
at 50% by weight, or from 20% to 40% by weight. 23. Composite material of any one of claims 1 to 22, in in which the inorganic particles comprise an inorganic compound of the type amorphous, ceramic or glass ceramic, for example, oxide, sulfide or oxysulfide. 24. Composite material of claim 23, in which the compound inorganic amorphous, ceramic or glass-ceramic type is an oxide. 25. Composite material of any one of claims 1 at 23, in in which the inorganic particles comprise a ceramic chosen from A1203, Mg2B205, Na20.2B203, xMgO=yB203.zH20, Ti02, Zr02, ZnO, Ti203, Si02, Cr203, Ce02, B203, B20, BrBi4114015, LLTO, LLZO, LAGP, LATP, Fe203, BaTiO3, y-LiA102, molecular sieves and zeolites (e.g. aluminosilicate, silica mesoporous), sulphide ceramics (such as Li7P3S11), glass ceramics (such such as LIPON, etc.), and other ceramics, as well as their combinations. 26. Composite material of claim 25, in which the ceramic is chosen from A1203, Mg2B205, Na20=2B203, xMg01/B203.zH20, Ti02, Zr02, ZnO, Ti203, Si02, Cr203, Ce02, B203, B20, SrBi4Ti4015, LLTO, LLZO, LAGP, LATP, Fe203, BaTiO3, y-LiA102, molecular sieves and zeolites (e.g., aluminosilicate, mesoporous silica), glass ceramics (such as LIPON, etc.), as well as their combinations. 27. Composite material of any one of claims 1 to 26, in which the inorganic particles are in the form of spherical particles, in rods, needles, nanotubes, or any combination thereof. 28. Composite material of any one of claims 1 to 27, in in which the inorganic particles comprise a compound chosen from compounds of formula:
Li1~zAlzM2-z(PO4)3 in which M is Ti, Ge or a combination thereof, and z is such that 0 < z < 1. 29. Composite material of claim 28, in which z is located in the interval from 0.1 to 0.9, or from 0.3 to 0.7, or from 0.2 to 0.4. 30. Composite material of any one of claims 1 to 27, in in which the inorganic particles comprise a compound chosen from compounds of formulas:
Li7-xLa3Zr2Mxx012 and Li3yLa(2/3)-yTi1- y’MYy’03 in which :
Mx is chosen from Al, Ga, Ta, Fe, and Nb;
MY is chosen from Ba, B, Al, Si and Ta;

x is such that 0 ~ x 5 1;
y is such that 0 < y <0.67; And y' is such that 0 É y'< 1. 31. Composite material of claim 30, in which x is located in the range from 0 to 0.5, preferably x is zero and Mx is absent. 32. Composite material of any one of claims 1 to 31, in which the content of inorganic particles is in the range from 1% to 95%
by weight, or from 5% to 90% by weight, or from 5% to 80% by weight, or from 5% to 70%
by weight, or from 5% to 60% by weight, or from 5% to 50% by weight, or from 5% to 40%
by weight, or from 5% to 25% by weight, or from 5% to 15% by weight. 33. Composite material of any one of claims 1 to 32, in in which the polymer is present and the composite material further comprises a plasticizing agent. 34. Composite material of claim 33, in the plasticizing agent is selected among glycol diether liquids (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, and others similar. 35. Composite material of claim 33 or 34, in which the agent plasticizer is present in the composite material at a concentration located In the range of 0.1% to 50% by weight, or 10% to 50% by weight, or 20% to 40%
in weight. 36. Composite material of any one of claims 1 to 35, further comprising a salt. 37. Composite material of claim 36, in which the salt comprises A
cation of an alkali or alkaline earth metal, preferably an alkali metal (of preferably Li), and an anion chosen from hexafluorophosphate anions (PF6-), bis(trifluoromethanesulfonyl)imide (TFSI-), bis(fluorosulfonyl)imide (FS1-), (flurosulfonyl)(trifluoromethanesulfonyl)imide ((FS1)(TFS1)-), 2-trifluoromethyl1-4,5-dicyanoimidazolate (TD1-), 4,5-dicyano-1,2,3-triazolate (DCTA-), bis(pentafluoroethylsulfonyl)imide (BETI-), difluorophosphate (DFP-), tetrafluoroborate (BF4-), bis(oxalato)borate (BOB-), nitrate (NO3-), chloride (C1-), bromide (Br), fluoride (F-), perchlorate (C104-), hexafluoroarsenate (AsF6-), trifluoromethanesulfonate (SO3CF3-) (Tf-), fluoroalkylphosphate [PF3(CF2CF3)31 (FAP-), tetrakis(trifluoroacetoxy)borate [B(OCOCF3)4]- (TFAB-), bis(1,2-benzenediolato(2-)-0.0')borate [B(C602)2]- (BBB-), difluoro(oxalato)borate (BF2(C204) -) (F0B-), an anion of formula BF204Rx- (where Rx = C2-4a1ky1e), and moon of their combinations, for example LiTFSI or LiFSI. 38. Solid electrolyte comprising a layer of composite material such as defined in any one of claims 1 to 37. 39. Electrochemical cell comprising a negative electrode, a electrode positive, and a solid electrolyte, in which at least one of the electrode positive, the negative electrode and the electrolyte comprises a composite material such as defined in any one of claims 1 to 37. 40. Electrochemical cell comprising a negative electrode, a electrode positive, and a solid electrolyte, in which the solid electrolyte is such as defined to claim 38. 41. Cell electrochemical comprising a negative electrode, an electrode positive, and a solid electrolyte, in which the electrolyte is such that defined at claim 38 and at least one of the negative electrode and the electrode positive comprises a composite material as defined in any one of the claims 1 to 37.
42.
Electrochemical cell of any one of claims 39 to 41, wherein the positive electrode comprises a positive electrode material possibly on a current collector, in which the material electrode positive electrode includes an electrochemically active positive electrode material. 42 43. Electrochemical cell of claim 42, in which the material electrochemically active positive electrode is chosen from phosphates of metals, lithiated metal phosphates, metal oxides, and oxides of lithiated metals. 44. Electrochemical cell of claim 42, in which the material electrochemically active positive electrode is LiM'PO4 where M' is Fe, Ni, Mn, Co, or a combination thereof, LiV308, V205F, LiV205, LiMn204, LiM"02, where M" is Mn, Co, Ni, or a combination thereof (such as NMC, LiMnxCoyNiz02 with x+y+z = 1), Li(NiMm)02 (where M" is Mn, Co, Al, Fe, Cr, Ti, Zr, or a combination thereof), sulfur, selenium or elemental iodine, iron(111) fluoride, copper(ll) fluoride, lithium iodide, materials carbon-based active materials such as graphite, cathode active materials organic (such as polyimide, poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PTMA), tetralithium perylene-3,4,9,10-tetracarboxylate (PTCLi4), naphthalene-1,4,5,8-tetracarboxylic dianhydride (NTCDA), perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), rr- dicarboxylates conjugates, and anthraquinone), or a combination of two or more of these materials when they are compatible with each other. 45. Electrochemical cell of any one of claims 42 to 44, in which the electrochemically active positive electrode material is below form of possibly coated particles (for example, of polymer, of ceramic, carbon or a combination of two or more of these). 46. Electrochemical cell of any one of claims 42 to 45, wherein the positive electrode material further comprises a material electronic conductor, for example, comprising at least one of the blacks of carbon (e.g. Ketjenblack TM or Super P TM ), acetylene blacks (e.g.
example, Shawinigan black in Denkan black"), graphite, graphene, fibers or carbon nanofibers (e.g., phase-formed carbon fibers gaseous (VGCFs)), carbon nanotubes (e.g. single-walled (SWNT), multi-wall (MWNT)) or metal powders. 47. Electrochemical cell of any of the claims 42 to 46, wherein the positive electrode material further comprises a binder. 48. Electrochemical cell of claim 47, in which the binder is a polymer as defined in claims 15 to 21, or a binder chosen from THE
rubber-like binders (such as SBR (styrene-butadiene rubber), NBR
(acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (acrylonitrile-butadiene rubber), epichlorohydrin), ACM (acrylate rubber)), or binders of the type fluoropolymers (such as PVDF (polyvinylidene fluoride), PTFE
(polytetrafluoroethylene), and combinations thereof), optionally comprising A
additive such as CMC (carboxymethylcellulose). 49. Electrochemical cell of any one of claims 42 to 48, wherein the positive electrode material further comprises a salt, inorganic particles of ceramic or glass type, or even others materials compatible active ingredients (for example, sulfur). 50. Electrochemical cell of any one of claims 42 to 48, wherein the positive electrode material further comprises the material composite defined in any one of claims 1 to 37. 51. Electrochemical cell of any one of claims 39 to 50, wherein the negative electrode comprises a material electrochemically active negative electrode. 52. Electrochemical cell of claim 51, in which the material electrochemically active negative electrode comprises a metal film comprising an alkali or alkaline earth metal. 53. Electrochemical cell of claim 52, in which the film metal comprises lithium comprising less than 1000 ppm (or less than 0.1 % by mass) of impurities. 54. Electrochemical cell of claim 52, in which the film metal comprises an alloy of lithium and an element chosen from metals alkalis other than lithium (such as Na, K, Rb, and Cs), alkaline metals earthy (such such as Mg, Ca, Sr, and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, SM, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel and germanium (e.g. Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, ln, Tl, Ni, or Ge). 55. Electrochemical cell of claim 54, in which the alloy comprises at least 75% by mass of lithium, or between 85% and 99.9% by mass of lithium. 56. Electrochemical cell of claim 51, in which the material electrochemically active negative electrode comprises a compound intermetallic (e.g. SnSb, TiSnSb, Cu2Sb, AlSb, FeSb2, FeSn2 and CoSn2), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (e.g. LiTi2(PO4)3), a metal halide (e.g.
example, a metal fluoride), a metal sulfide, a metal oxysulfide, A
carbon (e.g. graphite, graphene, reduced graphene oxide, a hard carbon, soft carbon, exfoliated graphite and amorphous carbon), silicon (Si), a silicon-carbon composite (Si-C), a silicon oxide (SKI), a silicon oxide-carbon composite (SiOx-C), tin (Sn), composite tin-carbon (Sn-C), a tin oxide (SnOx), a tin oxide-carbon composite (SnOx-C), and their combinations, when compatible. 57. Electrochemical cell of claim 56, in which the oxide of metal is chosen from the compounds of formulas M"bOc (where M" is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof; and b and c are numbers such that the c:b ratio lies in the interval from 2 to 3) (for example example, M003, M002, MoS2, V205, and TiNb207), spinel oxides (for example, NiCo204, ZnCo204, MnCo204, CuCo204, and CoFe204) and LiM"O (where M .......... is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof) (by example, a lithium titanate (such as Li4Ti5012) or a lithium oxide and molybdenum (such as Li2Mo4013)). 58. Electrochemical cell of claim 56 or 57, in which the electrochemically active negative electrode material is in the form of possibly coated particles (for example, polymer, ceramic, .. carbon or a combination of two or more of these). 59. Electrochemical cell of claim 58, in which the material negative electrode further comprises an electronic conductive material, by example, comprising at least one of the carbon blacks (for example, Ketjenblack TM or Super P TM ), acetylene blacks (e.g. black Shawinigan in .. black Denka TM), graphite, graphene, carbon fibers or nanofibers (by example, carbon fibers formed in the gas phase (VGCFs)), nanotubes of carbon (e.g. single-wall (SWNT), multi-wall (MWNT)) or metal powders. 60. Electrochemical cell of claim 58 or 59, in which the negative electrode material further comprises a binder. 61. Electrochemical cell of claim 60, in which the binder is a polymer as defined in claims 15 to 21, or a binder chosen from THE
rubber-like binders (such as SBR (styrene-butadiene rubber), NBR
(acrylonitrile-butadiene rubber), HNBR (hydrogenated NBR), CHR (acrylonitrile-butadiene rubber), epichlorohydrin), ACM (acrylate rubber)), or binders of the type fluoropolymers (such as PVDF (polyvinylidene fluoride), PTFE
(polytetrafluoroethylene), and combinations thereof), optionally comprising A
additive such as CMC (carboxymethylcellulose). 62. Cell electrochemical of any one of claims 58 to 61, wherein the negative electrode material further comprises a salt, inorganic particles of ceramic or glass type, or even others materials compatible assets. 63. Cell electrochemical of any one of claims 58 to 62, wherein the negative electrode material further comprises the material composite defined in any one of claims 1 to 37. 64. Electrochemical accumulator comprising at least one cell electrochemical as defined in any one of claims 39 to 63. 65.
Electrochemical accumulator according to claim 64, wherein said electrochemical accumulator is a lithium battery or a battery lithium-ion. 66. Use of an electrochemical accumulator according to claim 64 Or 65, in portable devices, for example mobile phones, cameras, tablets or laptops, in vehicles electric or hybrid, or in renewable energy storage. 67. Process for preparing a composite material as defined in one any of claims 1 to 37, comprising a step of mixing the inorganic particles, the fluorinated compound, and possibly the polymer. 68. Process according to claim 67, the mixing step comprising polymer and optionally a crosslinking agent. 69. Process according to claim 68, in which the mixing step comprises the crosslinking agent and the method further comprises a step of crosslinking of the polymer.